Effect of Polyoxymethylene (POM-H Delrin) offgassing within Pandora head sensor on direct sun and multi-axis formaldehyde column measurements in 2016 - 2019.

Analysis of formaldehyde measurements by the Pandora spectrometer systems between 2016 and 2019 suggested that there was a temperature dependent process inside Pandora head sensor that emitted formaldehyde. Some parts in the head sensor were manufactured from thermal plastic polyoxymethylene homopolimer (E.I. Du Pont de Nemour & Co., USA: POM-H Delrin®) and were responsible for formaldehyde production. Laboratory analysis of the four Pandora head sensors showed that internal formaldehyde production had exponential temperature dependence with a damping coefficient of 0.0911±0.0024 °C-1 and the exponential function amplitude ranging from 0.0041 DU to 0.049 DU. No apparent dependency on the head sensor age and heating/cooling rates was detected. The total amount of formaldehyde internally generated by the POM-H Delrin components and contributing to the direct sun measurements were estimated based on the head sensor temperature and solar zenith angle of the measurements. Measurements in winter, during colder (<10°C) days in general and at high solar zenith angles (> 75 °) were minimally impacted. Measurements during hot days (>28°C) and small solar zenith angles had up to 1 DU (2.69×1016 molecules/cm2) contribution from POM-H Delrin parts. Multi-axis differential slant column densities were minimally impacted (< 0.01 DU) due to the reference spectrum collected within a short time period with a small difference in head sensor temperature. Three new POM-H Delrin free Pandora head sensors (manufactured in summer 2019) were evaluated for temperature dependent attenuation across the entire spectral range (300 to 530 nm). No formaldehyde or any other absorption above the instrumental noise was observed across the entire spectral range.

Evaluating Sentinel-5P TROPOMI tropospheric NO2 column densities with airborne and Pandora spectrometers near New York City and Long Island Sound.

Airborne and ground-based Pandora spectrometer NO2 column measurements were collected during the 2018 Long Island Sound Tropospheric Ozone Study (LISTOS) in the New York City/Long Island Sound region, which coincided with early observations from the Sentinel-5P TROPOspheric Monitoring Instrument (TROPOMI) instrument. Both airborne- and ground-based measurements are used to evaluate the TROPOMI NO2 Tropospheric Vertical Column (TrVC) product v1.2 in this region, which has high spatial and temporal heterogeneity in NO2. First, airborne and Pandora TrVCs are compared to evaluate the uncertainty of the airborne TrVC and establish the spatial representativeness of the Pandora observations. The 171 coincidences between Pandora and airborne TrVCs are found to be highly correlated (r 2 =0.92 and slope of 1.03), with the largest individual differences being associated with high temporal and/or spatial variability. These reference measurements (Pandora and airborne) are complementary with respect to temporal coverage and spatial representativity. Pandora spectrometers can provide continuous long-term measurements but may lack areal representativity when operated in direct-sun mode. Airborne spectrometers are typically only deployed for short periods of time, but their observations are more spatially representative of the satellite measurements with the added capability of retrieving at subpixel resolutions of 250m×250m over the entire TROPOMI pixels they overfly. Thus, airborne data are more correlated with TROPOMI measurements (r 2 = 0.96) than Pandora measurements are with TROPOMI (r 2 = 0.84). The largest outliers between TROPOMI and the reference measurements appear to stem from too spatially coarse a priori surface reflectivity (0.5°) over bright urban scenes. In this work, this results during cloud-free scenes that, at times, are affected by errors in the TROPOMI cloud pressure retrieval impacting the calculation of tropospheric air mass factors. This factor causes a high bias in TROPOMI TrVCs of 4%-11%. Excluding these cloud-impacted points, TROPOMI has an overall low bias of 19%-33% during the LISTOS timeframe of June-September 2018. Part of this low bias is caused by coarse a priori profile input from the TM5-MP model; replacing these profiles with those from a 12 km North American Model-Community Multiscale Air Quality (NAMCMAQ) analysis results in a 12%-14% increase in the TrVCs. Even with this improvement, the TROPOMI-NAMCMAQ TrVCs have a 7%-19% low bias, indicating needed improvement in a priori assumptions in the air mass factor calculation. Future work should explore additional impacts of a priori inputs to further assess the remaining low biases in TROPOMI using these datasets.

The Ozone Water-Land Environmental Transition Study (OWLETS): An Innovative Strategy for Understanding Chesapeake Bay Pollution Events.

Coastal regions have historically represented a significant challenge for air quality investigations due to water-land boundary transition characteristics and a paucity of measurements available over water. Prior studies have identified the formation of high levels of ozone over water bodies, such as the Chesapeake Bay, that can potentially recirculate back over land to significantly impact populated areas. Earth-observing satellites and forecast models face challenges in capturing the coastal transition zone where small-scale meteorological dynamics are complex and large changes in pollutants can occur on very short spatial and temporal scales. An observation strategy is presented to synchronously measure pollutants 'over-land' and 'over-water' to provide a more complete picture of chemical gradients across coastal boundaries for both the needs of state and local environmental management and new remote sensing platforms. Intensive vertical profile information from ozone lidar systems and ozonesondes, obtained at two main sites, one over land and the other over water, are complemented by remote sensing and in-situ observations of air quality from ground-based, airborne (both personned and unpersonned), and shipborne platforms. These observations, coupled with reliable chemical transport simulations, such as the NOAA National Air Quality Forecast Capability (NAQFC), are expected to lead to a more fully characterized and complete land-water interaction observing system that can be used to assess future geostationary air quality instruments, such as the NASA Tropospheric Emissions: Monitoring of Pollution (TEMPO) as well as current low earth orbiting satellites, such as the European Space Agency's Sentinel 5-Precursor (S5-P) with its Tropospheric Monitoring Instrument (TROPOMI).

Evaluating the impact of spatial resolution on tropospheric NO2 column comparisons within urban areas using high-resolution airborne data.

NASA deployed the GeoTASO airborne UV-Visible spectrometer in May-June 2017 to produce high resolution (approximately 250 × 250 m) gapless NO2 datasets over the western shore of Lake Michigan and over the Los Angeles Basin. The results collected show that the airborne tropospheric vertical column retrievals compare well with ground-based Pandora spectrometer column NO2 observations (r2=0.91 and slope of 1.03). Apparent disagreements between the two measurements can be sensitive to the coincidence criteria and are often associated with large local variability, including rapid temporal changes and spatial heterogeneity that may be observed differently by the sunward viewing Pandora observations. The gapless mapping strategy executed during the 2017 GeoTASO flights provides data suitable for averaging to coarser areal resolutions to simulate satellite retrievals. As simulated satellite pixel area increases to values typical of TEMPO, TROPOMI, and OMI, the agreement with Pandora measurements degraded, particularly for the most polluted columns as localized large pollution enhancements observed by Pandora and GeoTASO are spatially averaged with nearby less-polluted locations within the larger area representative of the satellite spatial resolutions (aircraft-to-Pandora slope: TEMPO scale=0.88; TROPOMI scale=0.77; OMI scale=0.57). In these two regions, Pandora and TEMPO or TROPOMI have the potential to compare well at least up to pollution scales of 30×1015 molecules cm-2. Two publicly available OMI tropospheric NO2 retrievals are both found to be biased low with respect to these Pandora observations. However, the agreement improves when higher resolution a priori inputs are used for the tropospheric air mass factor calculation (NASA V3 Standard Product slope = 0.18 and Berkeley High Resolution Product slope=0.30). Overall, this work explores best practices for satellite validation strategies with Pandora direct-sun observations by showing the sensitivity to product spatial resolution and demonstrating how the high spatial resolution NO2 data retrieved from airborne spectrometers, such as GeoTASO, can be used with high temporal resolution ground-based column observations to evaluate the influence of spatial heterogeneity on validation results.

The first evaluation of formaldehyde column observations by improved Pandora spectrometers during the KORUS-AQ field study.

The Korea-United States Air Quality Study (KORUS-AQ) conducted during May-June 2016 offered the first opportunity to evaluate direct-sun observations of formaldehyde (HCHO) total column densities with improved Pandora spectrometer instruments. The measurements highlighted in this work were conducted both in the Seoul megacity area at the Olympic Park site (37.5232° N, 27.1260° E; 26 ma.s.l.) and at a nearby rural site downwind of the city at the Mount Taehwa research forest site (37.3123° N, 127.3106° E; 160ma.s.l.). Evaluation of these measurements was made possible by concurrent ground-based in situ observations of HCHO at both sites as well as overflight by the NASA DC-8 research aircraft. The flights provided in situ measurements of HCHO to characterize its vertical distribution in the lower troposphere (0-5km). Diurnal variation in HCHO total column densities followed the same pattern at both sites, with the minimum daily values typically observed between 6:00 and 7:00 local time, gradually increasing to a maximum between 13:00 and 17:00 before decreasing into the evening. Pandora vertical column densities were compared with those derived from the DC-8 HCHO in situ measured profiles augmented with in situ surface concentrations below the lowest altitude of the DC-8 in proximity to the ground sites. A comparison between 49 column densities measured by Pandora vs. aircraft-integrated in situ data showed that Pandora values were larger by 16% with a constant offset of 0.22DU (Dobson units; R 2 = 0.68). Pandora HCHO columns were also compared with columns calculated from the surface in situ measurements over Olympic Park by assuming a well-mixed lower atmosphere up to a ceilometer-measured mixed-layer height (MLH) and various assumptions about the small residual HCHO amounts in the free troposphere up to the tropopause. The best comparison (slope = 1.03±0.03; intercept = 0.29±0.02DU; and R 2 = 0.78±0.02) was achieved assuming equal mixing within ceilometer-measured MLH combined with an exponential profile shape. These results suggest that diurnal changes in HCHO surface concentrations can be reasonably estimated from the Pandora total column and information on the mixed-layer height. More work is needed to understand the bias in the intercept and the slope relative to columns derived from the in situ aircraft and surface measurements.